EP3524643B1 - Harzfolie auf polyalkylencarbonatbasis - Google Patents
Harzfolie auf polyalkylencarbonatbasis Download PDFInfo
- Publication number
- EP3524643B1 EP3524643B1 EP17887520.9A EP17887520A EP3524643B1 EP 3524643 B1 EP3524643 B1 EP 3524643B1 EP 17887520 A EP17887520 A EP 17887520A EP 3524643 B1 EP3524643 B1 EP 3524643B1
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- EP
- European Patent Office
- Prior art keywords
- resin
- polyalkylene carbonate
- carbon atoms
- carbonate
- film according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims description 156
- 239000011347 resin Substances 0.000 title claims description 156
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims description 101
- 229920001281 polyalkylene Polymers 0.000 title claims description 90
- 229920001470 polyketone Polymers 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 18
- -1 polyethylene carbonate Polymers 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000007860 aryl ester derivatives Chemical class 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 229920006026 co-polymeric resin Polymers 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 229920006027 ternary co-polymer Polymers 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 27
- 230000000704 physical effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 6
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 239000012785 packaging film Substances 0.000 description 4
- 229920006280 packaging film Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229930182843 D-Lactic acid Natural products 0.000 description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 229940022769 d- lactic acid Drugs 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- BCJPEZMFAKOJPM-UHFFFAOYSA-N 2-ethyl-3-methyloxirane Chemical compound CCC1OC1C BCJPEZMFAKOJPM-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2473/00—Characterised by the use of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08J2459/00 - C08J2471/00; Derivatives of such polymers
Definitions
- the present invention relates to a polyalkylene carbonate-based resin film comprising a polyalkylene carbonate-based resin in which physical properties of a polyalkylene carbonate resin have been complemented.
- Plastics are used as materials for various articles due to their ease of manufacture and convenience of use, and for example, they are used in various fields such as disposable articles such as packaging films, disposable cups and disposable dishes, as well as building materials and automobile interior materials.
- a polyalkylene carbonate resin has an advantage that due to its high oxygen barrier property and high elongation property, it can be used for various applications such as food packaging and industrial protective films.
- the polyalkylene carbonate resin has a problem that a tensile strength is relatively low compared to a high elongation property, and thus a blend resin in which a resin having excellent tensile strength (for example, polylactic acid) is mixed for improving a tensile strength is used.
- a resin having excellent tensile strength for example, polylactic acid
- the tensile strength can be improved by an additional resin, but to that extent, the elongation property of the polyalkylene carbonate is deteriorated, and the tear strength (split strength) is also decreased.
- workability is significantly deteriorated if torn at the time of packaging, and if torn after packaging, scratches are generated on the products during transportation. Therefore, a film having excellent tear strength even while having high tensile strength and elongation is required.
- compatibility between both polymers should be good in order to complement each other's physical properties.
- Compatibility means that when two polymers are mixed, the two polymers are uniformly mixed or dispersed. If the compatibility is decreased, physical properties of each polymer are expressed intactly, and thus each other's physical properties cannot be complemented. Therefore, various studies have been made on resins having excellent compatibility with polyalkylene carbonate while exhibiting the above-mentioned physical properties.
- Korean Patent Laid-open Publication No. 10-2014-0070706 discloses the use of a lactide copolymer which includes at least two block copolymer repeating units in which a hard segment of polylactide repeating units is combined at both terminal ends of a soft segment of polyether polyol repeating units, wherein the block copolymer repeating units are connected to each other via an urethane linking group derived from a polyhydric isocyanate compound.
- this method has to produce a copolymer having a novel structure, and is problematic in that the cost is increased compared to the use of polylactic acid.
- JPH101601 A discloses molded articles, including an inflation molding film, comprising a thermoplastic resin composition comprising 30 parts by weight polyketone having a constitutional unit of formula (1), 70 parts by weight polycarbonate, and 5 parts by weight of a block copolymer containing a carboxyl group.
- the present invention relates to a polyalkylene carbonate film comprising a polyalkylene carbonate resin having improved mechanical properties.
- one aspect of the present invention provides a polyalkylene carbonate-based film comprising a blend resin in which 75 to 99% by weight of a polyalkylene carbonate resin and 1 to 25% by weight of a polyketone resin are mixed, wherein the film has a tensile strength of 200 kgf/cm 2 to 300 kgf/cm 2 as measured by ASTM D 638.
- the blend resin may be prepared by mixing 80 to 90% by weight of a polyalkylene carbonate resin and 10 to 20% by weight of a polyketone resin.
- the polyalkylene carbonate resin may include a repeating unit represented by the following Chemical Formula 1.
- R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, at least two of R 1 to R 4 may be connected to each other to form a cycloalkyl group having 3 to 10 carbon atoms, and m is an integer of 10 to 1,000.
- the polyalkylene carbonate resin may be at least one selected from the group consisting of a polyethylene carbonate resin, a polypropylene carbonate resin, a polypentene carbonate resin, a polyhexene carbonate resin, a polyoctene carbonate resin, a polycyclohexene carbonate resin, and a copolymer resin thereof.
- the polyalkylene carbonate resin may have a weight average molecular weight of 50,000 g/mol to 500,000 g/mol.
- the polyketone resin may include a repeating unit represented by the following Chemical Formula 2: in Chemical Formula 2, R is a linear or branched alkylene having 1 to 10 carbon atoms; an arylene having 6 to 30 carbon atoms; an alkyl ether having 1 to 10 carbon atoms; an aryl ether having 6 to 30 carbon atoms; an alkyl ester having 1 to 10 carbon atoms; or an aryl ester having 6 to 30 carbon atoms, and n is an integer of 10 to 1,000.
- R is a linear or branched alkylene having 1 to 10 carbon atoms; an arylene having 6 to 30 carbon atoms; an alkyl ether having 1 to 10 carbon atoms; an aryl ether having 6 to 30 carbon atoms; an alkyl ester having 1 to 10 carbon atoms; or an aryl ester having 6 to 30 carbon atoms
- n is an integer of 10 to 1,000.
- the polyketone resin may be an aliphatic polyketone resin containing ethylene, propylene, isopropylene, or butylene units.
- the polyketone resin may be a binary copolymer or a ternary copolymer.
- the polyketone resin may have a weight average molecular weight of 10,000 to 1,000,000 g/mol.
- the polyketone resin may have a melt index (MI) of 3 to 8.
- an internal tearing strength of the polyalkylene carbonate-based film according to ASTM D 1004-03 may be 50 kg/cm to 80 kg/cm.
- an elongation of the polyalkylene carbonate-based film according to ASTM D 638 may be 300% to 500%.
- the mechanical properties can be improved simultaneously without deteriorating excellent elongation properties possessed by the polyalkylene carbonate resin.
- the polyalkylene carbonate-based resin film of the present invention is excellent in compatibility between the polyalkylene carbonate resin and the polyketone resin without another compatibilizer.
- the polyalkylene carbonate resin has a low glass transition temperature (Tg) of about 20°C and is fragile at a temperature equal to or lower than Tg, and has difficulty in producing into a film due to soft tackiness at a temperature equal to or higher than Tg.
- Tg glass transition temperature
- the present inventors have found that by including a blend resin in which the polyalkylene carbonate resin and the polyketone resin are mixed in a specific amount, mechanical properties can be remarkably improved while maintaining the inherent excellent physical properties possessed by the polyalkylene carbonate, thereby completing the present invention.
- the polyalkylene carbonate resin and the polyketone resin are mixed and used in the above-described specific ratio and their tensile strengths satisfy a specific range, it is excellent in compatibility without a compatibilizer commonly used in a blend resin, and thereby, it does not cause a problem that physical properties of the film are deteriorated due to the compatibilizer.
- the polyalkylene carbonate-based resin film according to one embodiment of the present invention comprises a blend resin in which 75 to 99% by weight of a polyalkylene carbonate resin and 1 to 25% by weight of a polyketone resin are mixed, and as each resin is included within the above content range, both elongation properties and mechanical properties can be realized at excellent levels.
- the polyalkylene carbonate resin and the polyketone resin are very excellent in compatibility.
- the blend resin may include 80 to 90% by weight of a polyalkylene carbonate resin and 10 to 20% by weight of a polyketone resin.
- the above-described effects can be further improved within the above content range.
- the polyalkylene carbonate resin when the polyalkylene carbonate resin is mixed in a small amount exceeding the content range of 75 to 99% by weight based on the total weight of the blend resin, there may be a problem that the elongation properties are deteriorated. Further, when the polyketone resin is contained in an excessive amount exceeding 1 to 25% by weight based on the total weight of the blend resin, there may be a problem that the tear strength is slightly lowered.
- the polyalkylene carbonate-based resin film according to one embodiment of the present invention has a tensile strength of 200 kgf/cm 2 to 300 kgf/cm 2 , preferably 230 kgf/cm 2 to 290 kgf/cm 2 as measured according to ASTM D 638.
- the film has excellent processability and is resistant to scratches and external impact even after applied to a product. Therefore, it is applied to an industrial packaging film within the above tensile strength ranges and exhibits excellent physical properties.
- the polyalkylene carbonate-based resin film according to one embodiment of the present invention may have an internal tearing strength according to ASTM D 1004-03 of 50 kg/cm to 80 kg/cm, preferably 60 kg/cm to 70 kg/cm. When the above-mentioned range is satisfied, the film is not easily torn even when it is applied to a product after processing step of the film and completion of the film, which is preferable.
- the polyalkylene carbonate-based resin film according to one embodiment of the present invention may have an elongation of 300% to 500%, preferably 350% to 450%, as measured according to ASTM D 638. When the above range is satisfied, the film is excellent in processability and can be applied to various products.
- the polyalkylene carbonate-based resin film according to one embodiment of the present invention includes a blend resin in which a polyalkylene carbonate resin and a polyketone resin are mixed.
- the polyalkylene carbonate resin is a noncrystalline polymer. Unlike an aromatic polycarbonate resin, which is a synthetic resin of a similar type, not only the polyalkylene carbonate resin is biodegradable and thermally decomposed at low temperatures, but also it is completely decomposed into carbon dioxide and water and there is no carbon residue. Moreover, the polyalkylene carbonate resin exhibits excellent elongation properties and has an advantage that it can be easily applied to industrial packaging materials.
- the polyalkylene carbonate resin may contain a repeating unit represented by the following Chemical Formula 1.
- R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms; at least two of R 1 to R 4 may be connected to each other to form a cycloalkyl group having 3 to 10 carbon atoms, and m is an integer of 10 to 1,000.
- the degree of polymerization (m) of the repeating unit represented by Chemical Formula 1 may be about 10 to about 1,000, preferably about 50 to about 500.
- the weight average molecular weight of the polyalkylene carbonate containing the repeating unit may be 50,000 to 500,000, and preferably 10,000 to 100,000. When the above-mentioned range is satisfied, it is mixed with the polyketone resin and can exhibit excellent compatibility, which is preferable.
- the polyalkylene carbonate resin may be a homopolymer containing a repeating unit represented by Chemical Formula 1; or a copolymer containing two or more kinds of repeating units belonging to the category of Chemical Formula 1, a copolymer containing an alkylene oxide repeating unit or the like together with the repeating unit represented by Chemical Formula 1.
- the polyalkylene carbonate resin may be a copolymer containing at least about 40% by weight, preferably at least about 60% by weight, and more preferably at least about 80% by weight of at least one of the repeating units represented by Chemical Formula 1.
- the method for preparing the polyalkylene carbonate is not particularly limited, and for example, the polyalkylene carbonate can be obtained by copolymerizing an epoxide-based compound with carbon dioxide. Alternatively, the polyalkylene carbonate can be obtained by a ring-opening polymerization of a cyclic carbonate. The copolymerization of the alkylene oxide and carbon dioxide may be carried out in the presence of a metal complex such as zinc, aluminum or cobalt.
- a metal complex such as zinc, aluminum or cobalt.
- the epoxide-based compound may be ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide or butadiene monoxide or the like, or alternatively two or more kinds of various epoxide-based compounds selected among them, but the present invention is not limited thereto.
- the polyalkylene carbonate resin may be, for example, a polyethylene carbonate resin, a polypropylene carbonate resin, a polypentene carbonate resin, a polyhexene carbonate resin, a polyoctene carbonate resin, a polycyclohexene carbonate resin, or a copolymer resin thereof, but is not limited thereto.
- the polyketone resin is a resin which is excellent in mechanical properties and low in moisture absorption, and thus has little dimensional change and little change in physical properties due to moisture absorption.
- the polyketone resin can be mixed with the above-mentioned polyalkylene carbonate resin within a specific amount range to realize excellent elongation properties and tear strength properties.
- the polyketone resin may include a repeating unit represented by Chemical Formula 2.
- R is a linear or branched alkylene having 1 to 10 carbon atoms; an arylene having 6 to 30 carbon atoms; an alkyl ether having 1 to 10 carbon atoms; an aryl ether having 6 to 30 carbon atoms; an alkyl ester having 1 to 10 carbon atoms; or an aryl ester having 6 to 30 carbon atoms
- n is an integer of 10 to 1,000.
- the preparation method of the polyketone resin is not particularly limited, and for example, the polyketone resin is prepared by the reaction of carbon monoxide and a compound containing an unsaturated double bond. Recently, it can be prepared in the form of an alternating copolymer in which repeating units composed of carbon monoxide and at least one or more ethylenically unsaturated hydrocarbon are alternately connected.
- the melt index (MI) of the polyketone resin may be 3 to 8, preferably 5 to 7.
- compatibility with the polyalkylene carbonate is excellent, and the processing processablity of the film can be improved.
- the polyketone resin is an aliphatic polyketone containing ethylene, propylene, isopropylene, or butylene units. It is more preferable to use form of a binary copolymer or a ternary copolymer containing at least one of these repeating units.
- the polyketone resin may have a weight average molecular weight of about 10,000 to about 1,000,000 g/mol, preferably about 50,000 to about 500,000 g/mol. When the weight average molecular weight is satisfied, it is preferable from the viewpoint of the processability at the time of production and improvement of mechanical properties of the film. Further, when the above range is satisfied, the polyketone resin can be mixed with the polyalkylene carbonate resin to exhibit excellent compatibility, which is preferable.
- the polyalkylene carbonate resin film may further contain about 1 to about 30 parts by weight of the polylactide resin based on 100 parts by weight of the polyalkylene carbonate resin.
- the thermal stability of the polyalkylene carbonate resin can be improved, and thereby kneading with the polyketone resin can be carried out more stably.
- the polylactide resin is contained in an excessively smaller amount than the above range, decomposition of the polyalkylene carbonate may occur at the time of kneading polyketone and polyalkylene carbonate at high temperature.
- the polylactide is contained in an excessively large amount than the above range, there may be a problem that the inherent physical properties of the polyalkylene carbonate are deteriorated.
- the polyalkylene carbonate-based resin film of the present invention includes a polyalkylene carbonate resin, a polyketone resin, and a polylactide resin in a specific ratio, it has less blocking phenomenon during processing and is also excellent in thermal stability, while having excellent mechanical properties. Accordingly, it can be preferably used for a semi-permanent use such as sheets, food packaging films, floor materials, electronic product packages, or automobile interior materials.
- lactides may be classified into L-lactide composed of L-lactic acid, D-lactide composed of D-lactic acid and meso-lactide composed of one L-form and one D-form. Further, a mixture of L-lactide and D-lactide in a ratio of 50: 50 is referred to as D,L-lactide or rac-lactide.
- L-lactide or D-lactide having high optical purity among these lactides, is polymerized, L- or D-polylactide (PLLA or PDLA) having high stereoregularity is obtained, and that the polylactide obtained in this way is rapidly crystallized and has high crystallinity compared to polylactide having low optical purity.
- the "lactide monomers" is defined as including all types of lactides regardless of the difference in characteristics of lactides according to the types thereof and the difference in characteristics of polylactides derived therefrom.
- the molecular structure of the polylactide may be that polymerized from L-lactic acid, D-lactic acid or L,D-lactic acid.
- the polylactide may be prepared by a process including the step of forming the repeating units described below by the ring-opening polymerization of lactide monomers.
- the polymer obtained after the completion of the ring-opening polymerization and the repeating unit formation process may be referred to as the polylactide.
- the category of lactide monomers may include all types of lactides as described above.
- the polylactide may have the degree of polymerization of preferably about 50 to about 500, and may have a weight average molecular weight of about 10,000 to about 1,000,000 g/mol.
- the polyalkylene cabonate resin composition may maintain the inherent physical properties of the polyalkylene carbonate, and obtain excellent thermal stability effect even during processing at a high temperature.
- polylactide may include all the polymers obtained after the completion of the ring-opening polymerization and the repeating unit formation process, for example, unpurified or purified polymers obtained after the completion of the ring-opening polymerization, polymers included in a liquid or solid resin composition before the formation of a product, polymers included in plastic or textile after the formation of a product, and the like.
- a method of directly polycondensing lactic acid and a method of ring-opening polymerizing lactide monomers in the presence of an organic metal catalyst are known.
- the method of ring-opening polymerizing lactide monomers is complicated and needs high cost compared to the polycondensation because lactide monomers must be first prepared from lactic acid, but a polylactide resin having a relatively large molecular weight can be easily obtained by the ring-opening polymerization of lactide monomers using a organic metal catalyst, and the polymerization rate thereof can be easily adjusted. Therefore, this method is commercially widely available.
- the polyalkylene carbonate-based resin film according to the present invention includes a blend resin having the above-mentioned composition, and the mixing method of the blend resin can be used without particular limitation as long as it is a method commonly used in the art. Specifically, mixing can be carried out by a Henzel mixer, a ribbon blender, a blender or the like to thereby obtain a uniform mixture. Further, as the melt kneading method, a VAN Antonie Louis Barye mixer, a single-screw compressor, a twin-screw compressor or the like can be used.
- the blend resin can be prepared into a film through injection molding, compression molding, injection-compression molding, gas injection molding, foam injection molding, inflation, T-die, calendar, blow molding, vacuum molding, extrusion molding, and the like.
- it can be prepared into a film according to T-die method.
- the thickness of the polyalkylene carbonate-based resin film according to the present invention is not particularly limited, and may be suitably selected in the range required to maintain the elongation properties and mechanical properties described above. Preferably, it may have a thickness of 0.1 ⁇ m to 1,000 ⁇ m, or a thickness of 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m.
- the polyalkylene carbonate-based resin film according to the present invention contains a blend resin of the above-mentioned components and has a specific physical property value, it can realize excellent mechanical properties without deteriorating elongation properties. Therefore, the production processability of the film is excellent, and scratches, breakage or cracks do not occur after application of the product, and thus can be advantageously applied to industrial packaging materials.
- Preparation Example 1 Preparation of polyalkylene carbonate resin (A1, PEC)
- a polyethylene carbonate resin was prepared by copolymerizing ethylene oxide and carbon dioxide using a diethyl-zinc catalyst through the following method ( Journal of Polymer Science B 1969, 7, 287 ; Journal of Controlled release 1997, 49, 263 ).
- Polylactide (NatureWorks PLA 3001D) was mixed with the polyethylene carbonate prepared above to prepare pellets so that the content of polylactide was 5 wt%.
- Polyketone resin Hyosung, M620A 20% was uniformly mixed with the polyethylene carbonate resin 80% (containing 5 wt% of NatureWorks PLA 3001 D) and dried in a vacuum oven at 40°C for 12 hours.
- a T-die film producing device was attached to a twin-screw extruder and the resultant product was extruded at about 165°C to 185°C to prepare a 20 mm T-die film.
- a T-die film was prepared in the same manner as in Example 1, except for that the components and content shown in Table 1 below were used.
- NatureWorks 4032D was used as the PLA resin.
- Example 1 A1/80 B1/20 - Example 2 A1/90 B1/10 - Comparative Example 1 A1/100 - - Comparative Example 2 A1/80 - C1/20 Comparative Example 3 A1/50 B1/50 -
- the tear strength, tensile strength and elongation were measured by the following method using UTM (Universal Testing Machine, Instron). The results are shown in Table 2 below.
- Example 1 and Comparative Example 2 a strand was produced using a die in a twin-screw extruder. SEM images of the prepared strand were taken to confirm a domain shape of the blend resin. The results are shown in FIGS. 1 and 2 .
- [Table 2] Category Tensile strength (kgf/cm 2 ) Elongation (%) Tear strength(kg/cm) Example 1 277 417 63 Example 2 220 502 54 Comparative Example 1 88 806 25 Comparative Example 2 167 283 45 Comparative Example 3 Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible. Film production is impossible
- Example 1 where PEC and PK are mixed and used within the range of the content according to the present invention, it can realize remarkably excellent mechanical properties (tensile strength and tear strength) as compared with Comparative Examples.
- excellent tensile strength and tear strength are achieved within the elongation range of 300% to 500%, which is a proper elongation range required for an industrial packaging film.
- Comparative Example 2 it is a conventional technique in which PLA is combined to complement the physical properties of PEC. Referring to the image of FIG. 2 , it can be confirmed that the compatibility is lowered and a clear interface exists. When the compatibility is lowered, the respective physical properties of the blend resin are expressed intactly when applied to the product, and thus there is a problem that each other's physical properties cannot be sufficiently complemented.
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Claims (10)
- Polyalkylencarbonat-basierter Film, umfassend ein Mischharz, in dem 75 bis 99 Gew.-% eines Polyalkylencarbonatharzes und 1-25 Gew.-% eines Polyketonharzes gemischt sind,
wobei der Film eine Zugfestigkeit von 200 kgf/cm2 bis 300 kgf/cm2, gemessen nach ASTM D 638, hat. - Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Mischharz durch Mischen von 80 bis 99 Gewichtsteilen eines Polyalkylenharzes und 10 bis 20 Gewichtsteilen eines Polyketonharzes hergestellt wird.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Polyalkylencarbonatharz eine Wiederholungseinheit einschließt, dargestellt durch die folgende chemische Formel 1
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Polyalkylencarbonatharz zumeist eines ist, ausgewählt aus der Gruppe, bestehend aus Polyethylencarbonatharz, Polypropylencarbonatharz, Polypentencarbonatharz, Polyhexencarbonatharz, Polyoktencarbonatharz, Polycyclohexencarbonatharz und einem Copolymerharz davon.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Polyalkylencarbonatharz ein Gewichtsmittel des Molekulargewichts von 50.000 g/mol bis 500.000 g/mol hat, gemessen mittels Gelpermeationschromatographie GPC.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Polyketonharz eine Wiederholungseinheit einschließt, dargestellt durch die folgende chemische Formel 2:ist R ein lineares oder verzweigtes Alkylen mit 1 bis 10 Kohlenstoffatomen; ein Arylen mit 6 bis 30 Kohlenstoffatomen; ein Alkylether mit 1 bis 10 Kohlenstoffatomen; ein Arylether mit 6 bis 30 Kohlenstoffatomen; ein Alkylester mit 1 bis 10 Kohlenstoffatomen; oder ein Arylester mit 6 bis 30 Kohlenstoffatomen, undist n eine ganze Zahl von 10 bis 1.000.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Polyketonharz ein aliphatisches Polyketonharz ist, das Ethylen, Propylen, Isopropylen oder Butyleneinheiten enthält.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei das Polyketonharz ein binäres Copolymer oder ein tertiäres Copolymer ist.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei eine innere Reißfestigkeit des Polycarbonatharz-basierten Films, nach ASTM D 1004-03, 50 kg/cm bis 80 kg/cm ist.
- Polyalkylencarbonat-basierter Film nach Anspruch 1, wobei eine Dehnung des Polyalkylencarbonat-basierten Films, nach ASTM D 638, 300% bis 500% ist.
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